Chromiferous dyestuffs and process of making same



Patented July 28, 1936 *UNiTED STATE-s PATENT oFFIcE "'iiimoMIFERoUs DYESTUFFS AND PRO or MAKING SAME No Drawing. Application June 7,1933, Serial No. 674,770. In Switzerland" July 20, 1932 20 Claims. (01. 26012) This invention relates to the manufacture of dyestuffs by treating, in the absence of an organic base, with an agent yielding chromium an azo-dyestufi of the general formula,

10 wherein R1 is an aryl radica-lwhich in the one ortho-position to the azo-bridge contains a'carboxyl-group and in the other ortho-position to the azo-bridge contains 'no hydroxyl-group and 15 R2 is hydrogen, alkylor aryl, and wherein at least one of the ,aryl residues must contain at least one sulfonic group as a substituent.

The parent dyestufis for the manufacture may be made by coupling a 'diazotized' ortho-aminoarylcarboxylic acid, which contains in the orthoposition to the amino-groupnohydroxyl-group, with one of the various B-methylpyrazolones, the ortho-aminoar ylcarboxylic acid or the 3-methylpyrazolone being so selected that the azo-dyestufi obtained contains at least one sulio-group.

As suitable diam-components for making these parent dyestuffs there come into question, for example, the diazo-compounds from 2-aminobenzene 1 carboxylic acid, 2-amino-naphthalene-3-carboxylic acid, 1'-aminonaphthalene-2- carboxylic acid, -chloroor 5-bromo-2-aminobenzene-l-carboxylic acid, 4- or 5-sulfo-2- aminobenzene-l-carboxylic acid, 4-methoxyor 4-ethoxy-2-aminobenzene-l-carboxylic acid, 4- hydroxy-Z-aminobenzene-l carboxylic acid, 4- nitro-2-aminobenzene-l-carboxylic acid, S-Sulfo- 5-chloro-2-aminobenzene-l-carboxylic acid and 3- or 4-sulfo-5-methyl-2 aminobenzene-l-carboxylic acid. I

40 As coupling components for making these parent dyestuffs there come into question, for example,'the 3-methyl-5-pyraz'olone, the l-ethyl-3- methyl-5-pyrazolone, the lz3-dimethyl- 5-pyrazclone and also the l-aryl-B-methyl- 5 pyrazo- -lones, which, forexample, can be madeirom the following amines: aniline, toluidine,'xy lidine, 1-

or 2-naphthylamine, aniline-2,5-disulfonic acid,

2'-methyl-4-sulfo aniline, 2-chlorani1'ine, 2-chlor aniline-S-sulionic acid, v sulfanilic acid, 2,4-

dimethyl-l-aminobenzene-fi-sulfonic acid metanilic acid, 2-methyl-j5-sulfo-aniline, 3 -carboxy-l-hydroxy 1 aminobenzene, 2-naphthylamine-fi-su'lfonic acid, 4- or "5' sulfo-2-amino- 'benzeneel-carboxylic acid, Z-hy'drOxy-3-amino "5-lsulfob'enz'ene-l carboxylic" acid "and 2 -hydroxy-3-sulfo-5-aminobenzene-l-carboxylicacid.

As agents yielding chromium with which the azo-dyestufis of the above general formula are treated, may be used both inorganic'chromium salts, such as chromiumfluoride, chromium sulfite, chromium chloride and organic chromium 5 salts, such as chromium acetate or chromium formate.

The dyestufi may be treated with the agent yielding chromium in acid, neutral or alkaline medium, with or without an addition other than 10 an organic base and in the open or under pressure.

The chromiferous dyestufis obtained inaccordance with the invention dye' y'erylfvari0us tints. They are characterized byre'inarkable fastness, particularly to mi1ling and light, and also by very good levelling properties." The dyestufis may be used for dyeing material of any kind, such as wool,'silk, cotton leather, artificial silk, whether derived from regenerated cellulose or cellulose esters or ethers, and lacquers made from a cellulose base or a natural or artificial resin basej or they may be used as pigments or inprinting.

The following examples illustrate the invention, the pa'rts being by weight:-

, Example 1 V 25.3 parts of the azo-dyestuff of the formula N=N C-(fi-CH: 01 coon HO-L-C N Boss and the dyeing has good fastness tdmilling, very good uniformity and exceuent mama to light.

for about 12 hours.

Example 2 24.3 parts of the azo-dyestufi of the formula HOaS N=NCC-OH:

COOH HO-O N other chromium salts.

Example 3 A solution of 21.6 parts of the azo-dyestufi' of the formula COOH HO-C N from diazotized 4-sulfo-2-aminobenzene-l-carboxylic acid and 1-(2'-ch1oro-)pheny1-3-methyl- 5-pyrazo1one in 400 parts of water is mixed with a solution of chromium fluoride, corresponding with 4.6 parts of chromium oxide, and the mixture is boiled for about 12 hours in a reflux apparatus. The chromium compound is salted out. When dry it is a dark yellow powder, soluble in Water to a yellow solution and dyeing wool in an acid bath reddish-yellow tints characterized by a remarkable fastness to light.

Example 4 25.3 parts of the azo-dyestufi of the formula COOH HO-O N HOaS ols

-from diazotized 4-sulfo-2-aminobenzene-1-carboxylic acid and 1- (2-chloro-5'-sulfo-) -3-methyl- S-pyrazolone are dissolved in about 200 parts of water and, after addition of 4.6 parts of chromium oxide in the form of a chromium ,sulfate, solution, the whole is boiled for several hours in a reflux apparatus. The chromed dye stuff is salted out. After drying, it is a dark yellow powder, soluble in water, in sodium carbonate solution of 10 per cent. strength, in caustic soda solution of 10 per cent. strength and in concentrated sulfuric acid to a yellow solution in each case. It dyes wool in an acid bath reddishyellow tints of good fastness to light.

. Example 5 18.9 parts of the azo-dyestufi of the formula OOOH HO-C from diazotized 4-sulfo-2-aminobenzene-l carboxylic acid and 1-phenyl-3-methyl-5-pyrazolone are dissolved in 500 parts of water and the solution is boiled for several hours in a reflux apparatus with chromium fluoride corresponding with 4.6 parts of chromium oxide. The chromed dyestuif is then salted out. to a yellow solution and dyes wool in an acid bath reddish tints of good properties of fastness.

Example 6 A concentrated aqueous solution of 22.9 parts of the azo-dyestuff of the formula from diazotized V 4-sulfo-2-aminobenzene-l-car- .boxylic acid and 1-(4-sulfo-)phenyl-3-methyl- 5-pyrazolone is heated to boiling in a reflux apparatus for several hours with 4.6 parts of chromium oxide in the form of chromic oxalate.

.The chromium which has not been taken up by vthe dyestuff, is separated by addition of alkali and the filtrate is evaporated to dryness. The dark yellow powder thus obtained dissolves in water to a yellow solution. The chromed dyestufi dyes wool in an acid bath reddish-yellow tints which are very uniform and excellently fast to light, as well as of good fastness to milling.

Chromium compounds dyeing very fast reddish-yellow tints are also obtained'by treating It dissolves in water with an agent yielding chromium the azo-dyestufi' from diazotized 2-aminobenzene-1-carboxylic acid and 1-(2'-methy1-4sulfo-)phenyl- 3-methyl-5-pyrazolone; from diazotize d 4-sulf0- 2-aminobenzene-l-carboxylic acid and '1-(2 ,4"- dimethyl 6'- sulfophenyl-3i-methyl-5-pyrazo- .lone; from diazotized 4-sulfo-2-aminobenzene-1 carboxylic acid and 1-(3- sulfo-)phenyl-3- methy1-5-pyraz'olone, and from diazotized 4- sulfo-2-aminobenzene-l-carboxylic acid and 1- (2'-methy1-5-su1fo-) phenyl-3-methy1-5-pyrazo- 4 lone. v

gem-see COOH HO-C N SOsH nos

made in the usual manner from 18L parts-of 4 ethoxy-2-amino-1-benzoic acid and- 340 par-ts of 1- (2' ,5"-disulfo-) phenyl-3 methy1 5-pyrazolone together with 5000' parts of water and'80'0 parts of a solution of chromium sulfate, corre spending with 84 parts of chromium oxide, are heated together to boiling for a long time in a reflux apparatus. When chroming is complete, the dyestufi solution is made feeblyalkaline with sodium carbonate, filtered and the'filtrate evaporated to dryness in a vacuum. The dyestufi thus obtained is a yellow-brown powder soluble in water, sodium carbonate solution of 10' per cent. strength, caustic soda solution of 10 per cent. strength and concentrated sulfuric acid to a yellow solution in each case. It dyes wool in a sulfuric acid bath very uniform greenish yellow tints. The dyeings are characterized by a very good fastness to light and a good fastness to milling.

What we claim is:

1. Process for the manufacture of chromiferous dyestufis, comprising treating, in the absence of organic bases, with agents yielding'chromium, azo-dyestuffs of the general formula HO-C N wherein R1 is a sulfonated aryl radical containing a carboxyl-group in one ortho-position to the azo-bridge and no hydroxyl-group in the other ortho-po'sition tothe azo-bridge, a'nd-{Rzis-a member ofQthe group consisting of hydrogen, alkyl and aryl.

3. Process for the manufacture of chromiferous dyestufis; comprisingtreating, inthe absence wherein n: a membr'of the 'g'iaup consisting wherein a; mammal;

or" drg'a' bases;- wins agents yielding chromium, azo dyestuns ee the genera formula I Ri-N=N C --C,-C H:-

wherein R1 is anaryl radical, containing .a carboxyl-groupj in one rthQ-msition' to? the aid- 10 bridge aiidnb nya'rexyhgreu n the other orthoposition totne 'azo bridge; and R2 is a; 's'ulf'onated aryl radica li. V I.

4. Process forthe manufacture of chromifer ous dyestuffs, comprising treating, in the ab- 15 sence of organic bases, withagent's yielding chromium, azo-dye'stufi's'of the general formula it" N wherein; R1. is aphenyl, radicalcontaining in the on ortfimnosiuenra the amend-gee carbon lgr ours andiinui" otne cu ic-marina tothe'a'zoothe eel N/ of hydrogen alkyfandi phenyl.

, -45 6. Processi fof the manufacture or catamaran ous dyestufis, comprising treating in the absence ofbrganicpases, agentsv yielding chromium, azo-dyestufis of the general rename Hots g 7-; Process; forth'e-fii' iifacture often-restarous dyestufi, comprising treating, iii" the" atsence or organic oasegwnn; agent's yield iii? chromium, 66

the ai'zd dystlifi of the formula,

CHI

SOaHQ '8 Proces for the manufacture Oren-mutterous"'-dye"stufi, comprising" treating, in ab 5 sence of; organicbases, with: agentsyielding chro- COOH Holl R: wherein Rz.'is. a 'sulfo nated a'rylradical'. '91 Process for the manufacture for chromiferous 'dyestufis ,'coinprising treating, in"the absenceof organic bases, withagents yielding chromium,the azo-dyestuffrof the formula H HOaS 10., Chromiferous dyestufl's obtained by treating, in the absence of organic Lbases,,jwith agents yielding chromium, az'o-dyestufis of the general formula H wherein R1 is an aryl radical containing in the one'ortho-position to the azo-bridge a. carboxyl group and in the other ortho-position to the axebridge no hydroxyl-group, R2 is a member of the group consisting of hydrogen, alkyl and aryl, and wherein at leastone of the aryl radicals contains at least one sulfonic group as a substituent, which products are dark yellow to yellow brown powders dissolving, in water to yellowsolutions, anddyeing the fiber goldenyellow to reddish yellow tints of very good fastness properties. f 11.- Chromiferous dyestuffs obtained by treating, in the absence of organic bases, with-agents yielding chromium, azo-dyestufis of the general wherein R1 is an aryl radical containing a carboxyl-group inone ortho-position to the ambridge and no hydroxyl-group in the otherorthoF position to the azo bridg'e, and R2 is a sulfonated aryl radical.

13. Chromifer'ousdyestuifs obtained by treating, in the absence of organic bases, with agents yielding chromium, azo-dyestuffs of the general formula 4 wherein R1 is a phenyl radical containing in the one ortho-position to the azo-bridge a carboxylgroup and in the other ortho-position to the ambridge no, hydroxylgroup, R2 is a member of the group consistingof hydrogen, alkyl and phenyl, and wherein at least one of the phenyl radicals contains at leastone sulfonic group as a substituent,.which products are dark yellow to yellow brown powders dissolving in water to yellow solutions, and dyeing the fiber golden yellow to reddish yellow tints of very good fastness properties. w

14. Chromiferous dyestufis obtained by treating, inthe absence of organicbases, with agents yielding chromium, azo-dyestufis of the general formula coon HO-ll N wherein R2 is a member of the group consisting of hydrogen, alkyl and phenyl, which products are dark yellow powders dissolving in water to yellow solutions and dyeing the fiber reddish yellow tints of very good fastness properties.

15; Chromiferous dyestuffs obtained by treating, in the absence of organic bases, with agents yielding chromium, azo-dyestuifs of the general formula wherein R2 is a phenyl radical, which products are-dark yellow powders dissolving in water to yellow solutions and dyeing thefiber reddish yellow tints of very good fastness properties.

16. A chromiferous dyestuff obtained by treating, inthe absence of organic bases, with agents yieldingchromium, an'azo-dyestuff of the formula 1 1 which product is a dark yellow powder dissolving inwater to a yellow solution and dyeing the fiber reddish yellow tints of very good fastness properties.

i 'L -Qhromiferousdyestuffs obtained by treat ing, in the absence of organic, bases, with agents yielding chromium, azo-dyestufis of the general formula.

COOH HO- N 19. Process for the manufacture of a chromiferous dyestuif, comprising treating, in the absence of organic bases, with agents yielding chromium, the azo-dyestufi of the formula COOH H0- 20. Chromiferous dyestuffs obtained by treating, in the absence of or anic bases, with agents yielding chromium, the azo-dyestutf of the formula 00 OH HO- FRITZ S'I'RAUB. ERNST BRUNNER. WILLI WIDMZER. 

